Process for preparing pressure sensitive adhesives

ABSTRACT

In a process for preparing a pressure sensitive adhesive emulsion containing a polymer having a Tg of -10° C. or below which comprises polymerizing in an aqueous emulsion (a) an alkyl acrylate or vinyl ester, (b) an olefinically unsaturated carboxylic acid and (c) a polyolefinically unsaturated monomer for enhancing cohesive strength of the polymer, the method for enhancing the shear resistance of the pressure sensitive adhesive polymer which comprises 
     (1) forming an aqueous suspension reaction mixture comprising a stabilizing agent and at least a portion of the alkyl acrylate or vinyl ester, 
     (2) initiating the reaction mixture by the addition of a free radical source at a temperature from about 10°-40° C. and bringing the reaction mixture to a reaction temperature of from 45°-85° C. within a period of not more than 2 hours with the reaction temperature exceeding the initiation temperature by at least 15° C., 
     (3) adding the olefinically unsaturated carboxylic acid monomer and the polyolefinically unsaturated monomer at a substantially uniform rate such that the major portion of the carboxylic acid and polyolefinically unsaturated monomers has been added by the time the alkyl acrylate and vinyl ester content as free monomer in the reaction mixture has been reduced to a level of less than about 10 wt % of the mixture, and 
     (4) continuing polymerization of the reaction mixture until the alkyl acrylate and vinyl ester content as free monomer in the reaction mixture is reduced below about 1 wt %.

TECHNICAL FIELD

This invention relates to a method for preparing a pressure sensitive adhesive emulsion comprising a polymer system having good tack and peel strengths and enhanced shear strength.

BACKGROUND OF THE INVENTION

Aqueous or solvent based pressure sensitive adhesives are well-known and have found application in a variety of areas such as, for example, in the manufacture of tapes and labels. Good pressure sensitive adhesives have immediate adhesion to a surface which property is often referred to as "quick tack". They also require good resistance to failure when subjected to shearing forces after application. This property is referred to as "shear strength" or "shear resistance". They must also have excellent bond strength which is referred to as "peel". In the past commercial adhesives have generally comprised an acrylate ester or vinyl ester based polymer system with various amounts of other monomers, for example, polyfunctional adhesion promoting monomers, added to give desired properties.

Recent developments in the disposable diaper field have created a demand for pressure sensitive tapes, but many pressure sensitive adhesives are not suited for this use because the adhesives cannot tolerate the shear forces associated with that application. Although attempts have been made to enhance the shear strength of the polymer system, the quick tack and peel values of the resulting adhesion generally diminish with the increase in shear strength.

Another commercial area requiring exceptional pressure sensitive adhesives is the permanent label field. These labels must adhere well and retain their bond formation. High shear resistance is required since these labels quite often are exposed to high shear forces.

The following patents disclose a variety of pressure sensitive adhesives which are considered to be acrylic ester or vinyl ester based systems. Representative patents include:

U.S. Pat. No. 3,257,478 discloses pressure sensitive adhesives comprising vinyl acetate, octyl acrylate, ethyl acrylate and maleic anhydride. In addition, crosslinkable monomers such as N-methylolacrylamide are included.

U.S. Pat. No. 3,654,213 discloses a pressure sensitive adhesive comprising a polymer base of 2-ethylhexyl acrylate, vinyl acetate, acrylic acid and a mixed vinyl ester of an alkanoic acid containing 10-12 carbon atoms.

U.S. Pat. No. 3,697,618 discloses an acrylic pressure sensitive adhesive consisting of a vinyl ester of a saturated monocarboxylic acid, e.g. vinyl acetate, an alkyl acrylate, e.g. one having from 4-14 carbon atoms such as 2-ethylhexyl acrylate or dodecyl acrylate, and an alpha,beta-ethylenically unsaturated dicarboxylic acid with the vinyl acetate being present in a proportion of from 20-60 wt %, at least 35 wt % alkyl acrylate and from about 0.3 to 5 wt % acid.

U.S. Pat. No. 3,890,292 discloses a pressure sensitive adhesive comprising an alkyl acrylate, an alpha,beta-unsaturated carboxylic acid such as acrylic or methacrylic acid, a vinyl ester, e.g. vinyl acetate, and a plasticizer such as dibutyl phthalate. Emulsion polymerization techniques are employed.

U.S. Pat. No. 3,971,766 discloses a pressure sensitive adhesive containing a copolymer of an alkyl acrylate with 2-6 mole % acrylic or methacrylic acid and 0.002 to 0.05 mole % of a polyfunctional unsaturated monomer, e.g. diallyl phthalate or polyethylene glycol dimethacrylate for imparting internal cohesive strength.

U.S. Pat. No. 3,998,997 discloses pressure sensitive adhesives of interpolymers of acrylates and acrylic acid using a di-, tri-, or tetrafunctional vinyl crosslinking agent to enhance the cohesive strength of the polymer. The pressure sensitive adhesives are formed by emulsion polymerization with anionic, cationic, nonionic or amphoteric-type emulsifiers and surfactants suggested as being effective stabilizers for the polymerization medium.

U.S. Pat. No. 4,185,050 discloses a pressure sensitive adhesive comprising a terpolymer of an alkyl acrylate, a vinyl ester and an ethylenically unsaturated carboxylic acid. The pressure sensitive adhesive comprising a blend of a plurality of terpolymers formed from the above monomers with each terpolymer having a specific molecular weight range.

U.S. Pat. No. Re. 24,906 discloses an acrylic-based pressure sensitive adhesive formed by polymerizing a non-tertiary acrylate ester with a copolymerizable monomer having strongly polar groups such as acrylic or methacrylic acid. Typical esters employed are isoamyl acrylate, 2-ethylbutyl acrylate and 2-ethylhexyl acrylate. The polymers are produced by emulsion polymerization.

The inventor is also aware of a process to produce vinyl acetate-ethylene adhesive emulsions having a Tg of about -5° to +25° C. The polymerization of a recipe of vinyl acetate, ethylene, water, stabilizer and reducing agent is initiated at a temperature of 25° C. and a pressure below the operating pressure. The heat of reaction is utilized to achieve the operating temperature and operating pressure.

U.S. Pat. No. 4,332,850 discloses a method for preparing vinyl acetate-ethylene copolymer emulsions particularly adapted for the preparation of nonwoven goods. The process for enhancing the water absorptivity of the copolymer comprises pressurizing the reactor with ethylene, initiating the polymerization reaction by adding catalyst at a temperature from about 10°-35° C. and bringing the reaction mixture to a reaction temperature of 45°-85° C. and operating pressure within 2 hours or less with the reaction temperature exceeding the initiation temperature by at least 20° C.

SUMMARY OF THE INVENTION

The invention relates to a method for enhancing the shear strength of a pressure sensitive adhesive copolymer. The process provides a basic polymer system for pressure sensitive adhesives comprising an interpolymer of an alkyl acrylate or vinyl ester, or both, an olefinically unsaturated carboxylic acid comonomer, and a polyolefinically unsaturated copolymerizable monomer for enhancing cohesive strength of the interpolymer. The improvement in the polymer system resides in the method for forming the polymer system by aqueous emulsion polymerization techniques which method comprises

(a) forming an aqueous suspension reaction mixture comprising a stabilizing agent and at least a portion of the alkyl acrylate and/or vinyl ester,

(b) initiating the reaction mixture by the addition of a free radical source at a temperature from about 10°-40° C. and bringing the reaction mixture to a reaction temperature of from 45°-85° C. within a period of not more than about 2 hours with the reaction temperature exceeding the initiation temperature by at least 15° C.,

(c) adding the olefinically unsaturated carboxylic acid and the polyolefinically unsaturated monomers at a substantially uniform rate such that the major portion of the carboxylic acid and the polyolefinically unsaturated monomers has been added by the time the alkyl acrylate and vinyl ester content as free monomer in the reaction mixture has been reduced to a level less than 10 wt % of the mixture, and

(d) continuing polymerization of the reaction mixture until the alkyl acrylate and vinyl ester content as free monomer in the reaction mixture is reduced below about 1 wt %.

Pressure sensitive adhesive compositions containing copolymers produced by this method demonstrate an unexpectedly improved shear strength without any substantial sacrifice in peel or quick tack strength associated with the adhesive.

As an additional advantage such pressure sensitive adhesives can be water based and designed for easy and efficient application.

A further advantage is a shortened reaction time since the polymerization is carried out under conditions normally allocated to heat-up. The prior art techniques of requiring heat-up to operating temperatures of from 50° to 70° C. prior to initiating require a time delay.

Also the process is energy efficient because the heat of reaction is used to bring the reaction mixture to the reaction temperature.

DETAILED DESCRIPTION OF THE INVENTION

There are many properties necessary for the commercialization of a pressure sensitive adhesive, but qualities which all pressure sensitive adhesives require are high bond strength, which is determined at two intervals, mainly when first applied to a surface and after cure or bond formation, and high shear strength. The two properties of bond strength are referred to as "quick tack" and "peel" strength, both of which must be high, for example about 4 pounds per linear inch, in order to be effective as a pressure sensitive adhesive for tapes, particularly in the disposable diaper tape field and for permanent labels.

The third quality of a commercial adhesive is that it must have excellent cohesive strength such that when a shear force is applied, it will retain its integrity. Commercial pressure sensitive adhesives should have a shear resistance of about 3000 minutes, and preferably above 6000 minutes when measured with a 500 gram weight and 0.5 inch by 0.5 inch contact. Many of the conventional acrylate polymer systems contain soft polymer segments, and although these systems exhibit good quick tack and peel strength, they often have extremely poor shear strength. Vinyl acetate often has been incorporated into the polymer system to enhance the cohesive strength of the polymer, but still the shear strength of the polymer was too low for some applications. Crosslinking monomers, for example diallyl phthalate, were also added to aid shear resistance.

The present invention affords a pressure sensitive adhesive polymer system which is an improvement over the conventional pressure sensitive adhesive systems prepared using conventional polymerization techniques, the improvement relating to increasing the shear strength of the polymer system without substantially affecting the other properties, namely tack and peel. The polymer in the present system is formed by emulsion polymerization techniques and resides in a series of polymerization steps which can be referred to as "cold initiation".

The polymer in the pressure sensitive adhesive prepared according to the method of the invention described in more detail hereinafter comprises any alkyl acrylate or vinyl ester monomer, or both, used in pressure sensitive adhesives. Types of alkyl acrylate esters commonly used are the C₂ -C₁₀ alkyl esters of acrylic and methacrylic acid. The vinyl esters include the esters of C₁ -C₄ alkanoic acids. Representative examples of alkyl esters of acrylic and methacrylic acid are butyl acrylate, amyl acrylate, hexyl acrylate, decyl acrylate, 2-ethylhexyl acrylate, butyl methacrylate, nonyl acrylate, and the like. Representative vinyl esters include vinyl propionate, vinyl butyrate and vinyl acetate which is the preferred vinyl ester.

Diesters can also be substituted for some or all of the alkyl acrylate esters in the practice of this invention. Thus, the diesters are the functional equivalent of the alkyl acrylates purposes of this invention. These esters are generally C₄ -C₁₄, preferably C₈ -C₁₂, alkyl diesters of alpha,beta-olefinically unsaturated dicarboxylic acids. These diesters are included for purposes of imparting quick tack to the adhesive. Exemplary of these diesters are dihexyl maleate, dihexyl fumarate, dioctyl maleate, dibutyl maleate, dioctyl fumarate, and the like. Since these monomers are included in the copolymer for purposes of imparting quick tack, they can be used in addition to or as a replacement for the alkyl acrylate. Although vinyl acetate can be substituted for the alkyl acrylate or the olefinically unsaturated dicarboxylic acid diester, it is preferred that the pressure sensitive adhesive polymer contain a substantial amount of alkyl acrylate or diester of an unsaturated dicarboxylic acid, or both, in addition to the vinyl ester in order to provide the good quick tack and peel properties. Accordingly, either of these esters can be combined with vinyl acetate to produce a polymer having the desired Tg range and softness for quick tack and peel. Dioctyl maleate has been found to be a particularly effective diester for use with vinyl acetate in preparing the pressure sensitive adhesives according to the invention.

Combinations of monomers are selected so that the polymer will have a "softness" to it at room temperature, which is manifested in a polymer Tg (glass transition temperature) of -10° C. or below. Typically, the Tg is about -20° to -45° C. in these polymer systems. Thus, when a hard polymer forming monomer is included in the system, it may be necessary to alter its effect somewhat by including a softer polymer forming monomer or to increase the amount of soft polymer forming monomer. For example, if a high proportion of vinyl acetate is used, which results in a tough polymer having reduced peel, it may be necessary to go to a higher molecular weight acrylate ester or diester in order to soften the polymer to the desired level.

The vinyl ester, alkyl acrylate ester and/or diester combination is incorporated into the polymer system in an amount from about 92 to about 99.4 wt % with the balance comprising other monomers including polyolefinically unsaturated and adhesion promoting monomers. In most cases the polymer will comprise from about 25 to 50 wt % vinyl acetate and from about 50 to 75 wt % alkyl acrylate or diester. Since high levels of vinyl acetate in the polymer reduce peel and quick tack, it is preferable to use less vinyl acetate and enhance the cohesive strength of the polymer through the addition of greater amounts of polyolefinically unsaturated copolymerizable monomer or stabilizing agents such as polyvinyl alcohol, hydroxypropylmethyl cellulose or ethoxylated acetylenic glycol which are the preferred stabilizing agents in the polymerization recipe.

A polyfunctional monomer is incorporated into the polymer system to enhance the internal cohesive strength of the pressure sensitive adhesive. This type of monomer internally crosslinks the polymer system as it is formed as opposed to crosslinking the polymer system after synthesis, as in a post-cure system. The preferred polyfunctional monomers are polyolefinically unsaturated monomers such as polyvinyl or polyallylic monomers. These monomers can be di-, tri- or tetra olefinically unsaturated systems and include divinyl benzene, divinyl adipate, diallyl phthalate, diallyl maleate, diallyl fumarate, triallyl cyanurate and the like. These polyfunctional monmomers are used in a small proportion, in generally from about 0.1 to 0.4 wt % of the polymer system. When more than 0.4 wt % of the polyfunctional monomer is used, as for example with a triallylic monomer, the cohesive strength of the polymer may be increased but often the peel strength is reduced. Higher levels of monomer may be required with the di-olefinically unsaturated system than with the tri- or tetra-olefinically unsaturated system in order to achieve cohesive strength.

A fourth component used in the manufacture of the pressure sensitive adhesive is an adhesion promoting olefinically unsaturated carboxylic acid. The monocarboxylic acid monomers conventionally used in the manufacture of pressure sensitive adhesives and used in this invention contain from about 3 to 6 carbon atoms. Examples of such unsaturated carboxylic acids suited for the polymer system are those of the acrylic acid series such as acrylic and methacrylic acid, crotonic acid, maleic acid and the like. For reasons of convenience, acrylic acid is the preferred monomer. The acid functionality is included in an adhesion promoting amount from about 0.5 to 3.0 wt % of the polymer system. The combination of carboxyl containing monomer plus polyolefinically unsaturated monomer enhances shear resistance with the acid functionality having a tendency to enhance peel strength and quick tack in addition to enhancing sheer resistance.

Monomers in the four classes described above are well known as illustrated in the prior art describing polymer systems for pressure sensitive adhesive application. Accordingly, polymer based systems describe in the patents in the "Background of the Invention" section of this application are incorporated by reference.

The polymers which are best suited for pressure sensitive adhesive application using preferred monomers have an "insolubles" (measured in toluene at reflux temperature and atmospheric pressure) of about 45-65 wt %. The insolubles of the polymer can be controlled within this range by varying the ratio of polyolefinically unsaturated monomer vis-a-vis the unsaturated carboxylic acid and by controlling the level of stabilizer and the ratio of components in the stabilizer system. For example, employing a high level of polyvinyl alcohol or hydroxypropylmethyl cellulose content or polyolefinically unsaturated monomer will tend to increase the insolubles content of the polymer as compared to polymers produced with a low level of these materials. Polymers having low insolubles, for example less than about 45 wt %, tend to have reduced shear strength.

A preferred polymer base for the pressure sensitive adhesive generally comprises by weight:

(a) 57-67% alpha,beta-olefinically unsaturated dicarboxylic acid diester, for example, dioctyl maleate,

(b) 32-42% vinyl acetate,

(c) 0.1 to 0.4% polyallylic monomer, particularly triallylcyanurate, and

(d) 0.5 to 3.0% olefinically unsaturated carboxylic acid, for example acrylic acid.

The stabilizer system for preparing the aqueous emulsion reaction mixture may comprise those emulsifying agents and protective colloids generally well known in the polymerization art such as, for example, polyvinyl alcohols, celluloses, ionic surfactants and nonionic surfactants. It is preferred, however, that the stabilizer system comprises 1-4% wt % of an ethoxylated adduct of a tertiary acetylenic glycol and 1-4% wt % polyvinyl alcohol or hydroxypropyl methyl cellulose, based upon the weight of the monomers.

The polyvinyl alcohol is a partially hydrolyzed polyvinyl alcohol having a degree of hydrolysis from about 80-90% as is typical of the polyvinyl alcohols used as protective colloids. The degree of polymerization should be about 200 to 2400.

In place of the partially acetylated polyvinyl alcohol hydroxypropyl methyl cellulose can be used. A suitable hydroxypropyl methyl cellulose is a water soluble protective colloid having 15-35% methoxyl substitution, 3-35 hydroxypropoxyl substitution and having a viscosity ranging from 3 to 75,000 cps as a 2 wt % aqueous solution. It is preferred that the methoxyl substitution be about 28-30%, the hydroxypropoxyl substitution be 7-12% and the viscosity be in the range of 4 to 6 cps, especially about 5 cps. The degree of methoxyl and hydroxypropoxyl substitution is determined by the standard testing method ASTM D2363.

The other component of the stabilizer system may be an octylphenoxy polyethoxy ethanol of the general formula R--PhO--(CH₂ CH₂ O)_(n) H where R represents a C₈ group, Ph represents phenyl and n is a number from 10 to 30 or, preferably, an ethylene oxide adduct of an acetylenic tertiary glycol structurally represented by the formula ##STR1## in which R₁ and R₄ are alkyl (C₃ -C₁₀) radicals and R₂ and R₃ are methyl or ethyl, and x and y have a sum in the range of about 10-60, inclusive. In the preferred cases, R₁ and R₄ are alkyl (C₃ -C₄) radicals and R₂ and R₃ are methyl groups. Further examples and synthesis techniques for the manufacture of these adducts are shown in U.S. Pat. Nos. 3,268,593 and 3,293,191 which are incorporated by reference.

Ethoxylated tertiary acetylenic glycols for emulsion polymerization are generally used as a mixture or combination comprising a highly ethoxylated system (30 moles) and one of lesser ethoxylation, for example, 30 moles and 10 moles, respectively. Often, as is known, the lesser ethoxylated system will precipitate out at polymerization temperatures of about 70° C. and thus it is coupled with a higher ethoxylated form since that form is thermally stable at reaction temperature. However, as is known the higher ethoxylated form has lower wetability than the lesser ethoxylated form and, therefore, a balance between the tertiary acetylenic glycols is selected to accommodate the reaction medium.

In the polymerization process, the ethylene oxide adduct of the acetylenic tertiary glycol is included in a proportion sufficient to enhance the shear strength, or shear resistance, of the resulting copolymer. Typically, this proportion is from about 1 to 4 wt % of the monomers, and preferably is about 2 to 3 wt %. When the concentration of the ethoxylated acetylenic glycol falls below about 1 wt % there is generally insufficient surfactant to substantially increase the shear resistance. when the concentration exceeds about 4 wt %, no significant advantages are achieved or believed to be observed in terms of overall properties of the pressure sensitive adhesive. It may be that shear resistance increases, but there could also be a decrease in peel strength.

The partially hydrolyzed polyvinyl alcohol or hydroxypropyl methyl cellulose, or a combination of the two, is included in the stabilizer system in a porportion of about 1 to 4 wt % of the monomers. With these protective colloids the polymerization tends to result in a polymer having higher insolubles than polymers produced without them. To produce the percent insoluble range desired in the adhesive, namely 45 to 65 wt % in toluene, the polyvinyl alcohol or hydroxypropyl methyl cellulose is included in a proportion of about 1.5 to 3.5 wt % of the monomers with the ethoxylated acetylenic glycol comprising 1.5 to 3.5 wt % of the monomers.

The essence of the invention for providing pressure sensitive adhesive polymers having enhanced shear resistance is the polymerization method incorporating a "cold initiation". The first step, as with most other aqueous emulsion processes, lies in the formation of an aqueous emulsion of vinyl acetate and/or alkyl acrylate and other components used in the reaction mixture. In this regard, water is first mixed with a stabilizer system, preferably the stabilizer systems described above. Other components, for example, buffers, may be added as needed to form a premix. The premix is then charged to the reactor and the vinyl acetate and/or alkyl acrylate ester added. Optionally, these monomers can be added to the premix. At least 10 wt % and preferably about 50 wt % of the ester monomers are added prior to initiation. Then the oxidizing agent of the redox initiator system is added to the reactor.

Free radical sources, e.g. redox systems, stabilizers and buffers used in the practice of this invention are conventional and used in conventional amounts although the preferred stabilizer systems comprise partially hydrolyzed polyvinyl alcohol or hydroxypropyl methyl cellulose in combination with an octylphenoxy polyethoxy ethanol or an ethoxylated tertiary acetylenic glycol. Examples of reducing agents include the sulfoxylates, bisulfites, and ferrous salts. Specific examples include sodium and zinc formaldehyde sulfoxylate. Oxidizing agents include hydrogen peroxide and t-butyl hydroperoxide.

Prior to initiation the reaction mixture is adjusted to a temperature of from about 10° to 40° C., preferably 25° to 35° C. After the reaction mixture is brought to this initial temperature, polymerization of the reaction mixture is commenced by the addition of the reducing component of the initiator. The reducing agent could be added to the premix and the oxidizing agent added to initiate the reaction. It is also possible that some other free radical generating source could simply be added to the reaction mixture. On initiation, the temperature of the reaction mixture begins to rise and on continued addition of reducing agent the temperature will increase rapidly. Reducing agent addition is adjusted to reach a reaction temperature of from about 45° to 85° C., typically 50° to 60° C., ideally about 55° C., within about 2 hours and preferably within 1 hour, and then it is added at a rate to maintain such a temperature. The reaction temperature is set to be at least 15° C., preferably at least 20° C., above the initiation temperature. The reactor is preferably initially purged of oxygen and then maintained under a nitrogen blanket at about atmospheric pressure.

Once the reaction temperature rises about one degree Centigrade upon initiation, the remaining esters monomers comprising vinyl ester, alkyl acrylate ester and/or diester, as well as the olefinically unsaturated carboxylic acid monomer and polyolefinically unsaturated monomer for enhancing adhesive strength are added in a delay mode, i.e. the continuous or intermittent addition at a substantially uniform rate over a period of time. Such a delay addition is desirable in view of the difference in polymerization rates of many of the various monomers. So it is preferable to delay the addition of those monomers having a fast polymerization rate into the polymerization medium. For example, the acrylic monomers have a reaction rate much faster than the vinyl acetate and are often delayed to the system during polymerization. Typically, the addition of the monomers is carried out so that the major portion, for example, greater than 75% and preferably all the monomer is added by the time the ester monomer content in the emulsion is reduced to a level less than about 10 wt % and preferably less than 3 wt %, based on the emulsion.

Those skilled in the art will readily recognize that with a pressure sensitive adhesive copolymer comprising only acrylate esters, i.e. no vinyl ester, all the ester monomer, olefinically unsaturated carboxylic acid and polyolefinically unsaturated monomer could be added initially in a batch process utilizing the cold initiation procedure which is the essence of the invention for enhancing shear strength.

The pressure sensitive adhesive polymer emulsions prepared according to the method of the invention are suitably used to prepare adhesive products by compounding with other well-known components in the art and can be applied by a variety of methods known to the art which, in general, involve coating and spraying. Specific examples of pressure sensitive adhesive products prepared by applying the emulsions of this invention to substrates include release liners, labels, decals and tapes.

The following examples are provided to illustrate embodiments of the invention and are not intended to restrict the scope thereof. All parts are listed as parts by weight, and all percentages are expressed as weight percentages unless indicated otherwise.

EXAMPLE 1

Runs 1-4 of this Example demonstrate the use of the typical polymerization process utilizing the reaction temperatures above about 50° C. commencing with initiation of the reaction, "hot initiation".

For Run 1 an aqueous pressure sensitive adhesive formulation was prepared by purging a one gallon stainless steel reactor with nitrogen. Then the reactor was initially charged with a mixture comprising:

    ______________________________________                                         COMPONENT           WEIGHT PARTS                                               ______________________________________                                         1.    10% aqueous VINOL ® 205.sup.a                                                                328.4                                                        solution                                                                 2.    Deionized water   700.0                                                  3.    Surfynol ® 485.sup.b                                                                         15.9                                                   4.    Surfynol ® 465.sup.c                                                                         33.3                                                   5.    0.1% aqueous solution of                                                                         11.4                                                         Fe.sub.2 (SO.sub.4).sub.3.7H.sub.2 O                                     6.    Vinyl acetate (VAc)                                                                              303                                                    7.    Dioctyl maleate (DOM)                                                                            518                                                    ______________________________________                                          .sup.a VINOL ® 205 is a partially hydrolyzed (87-89%) polyvinyl            alcohol marketed by Air Products and Chemicals, Inc.                           .sup.b Surfynol ® 485 is an ethylene oxide adduct of                       2,4,7,9tetramethyl decyne diol containing an average of 30 moles ethylene      oxide per mole of surface active agent and having a cloud point of about       100° C. marketed by Air Products and Chemicals, Inc.                    .sup.c Surfynol ® 465 is an ethylene oxide adduct of                       2,4,7,9tetramethyl decyne diol containing an average of 10 moles ethylene      oxide per mole of surface active agent marketed by Air Products and            Chemicals, Inc.                                                          

After the reactor was initially charged with components 1-7, the vessel was then sealed under a nitrogen atmosphere. The agitator, which was a turbine blade agitator, was set at a rotation rate of about 300 rpm. After a nitrogen purge 28.5 parts of a 10% solution of t-butyl hydroperoxide was pumped into the vessel. The agitator was increased to 800 rpm. The temperature was raised to 55° C. After the temperature had reached a steady state, a 4.4% aqueous solution of sodium formaldehyde sulfoxylate was introduced into the reactor at a rate of about 1.2 ml/min and polymerization was initiated at this time. Once the polymerization had been initiated, the rate of addition of sodium formaldeyde sulfoxylate was maintained at about 1.1 to 1.2 ml/min for a period of about 215 minutes. Upon initiation a delay feed monomer composition was introduced at a rate of about 7 ml/min. The delay feed monomer composition comprised 294.8 parts vinyl acetate, 509.8 parts dioctyl maleate, 16.4 parts acrylic acid and 4.10 parts triallyl cyanurate. The delay feed was about 880 ml and was added over a period of about 120 minutes. To maintain the reaction 115 ml of 10% t-butyl hydroperoxide catalyst were added over a period of 215 minutes.

The reaction proceeded in conventional emulsion polymerization manner with the process temperature being maintained at 55° C. by jacket temperature contol. After about 3 hours, the reaction exotherm decreased indicating the polymerization was about complete at which time a small amount (4.8 ml) vinyl acetate was added over a 5 minute period. The purpose of this addition was to remove any residual dioctyl maleate in the system. Once the polymerization was complete, the contents of the vessel were cooled to 30° C. and removed from the reactor. The resulting product was then adjusted with a 14% aqueous ammonium hydroxide solution to raise the pH from a level of about 2.5-4.2 to a range between 5.5 and 6.5. The resulting polymer was measured for percent insolubles by measuring solubility in toluene at reflux temperature at atmospheric pressure. It had percent insoluble of 43%. The Tg was about -23.5° C.

This procedure was repeated for Runs 2-4 with the only change being the substitution of the stabilization system as indicated in Table 1 for the polyvinyl alcohol/surfynol ethoxylated acetylenic diol blend.

                                      TABLE 1                                      __________________________________________________________________________                                SHEAR     180°                                                                          LOOP                                RUN INITIATION                                                                             STABILIZATION SYSTEM                                                                          RESISTANCE (hr)                                                                          PEEL (lb)                                                                            TACK (lb)                           __________________________________________________________________________     1   Hot     PVOH/Surfynol blend                                                                           44        5.5   4.5                                 2   Hot     PVOH/Triton ® blend.sup.a                                                                 9         4.6   2.8                                 3   Hot     ME-5.sup.b /Surfynol blend                                                                    124       3.9   4.3                                 4   Hot     ME-5/Triton blend                                                                             29        4.3   3.7                                 5   Cold    PVOH/Surfynol blend                                                                           232       5.0   4.1                                 6   Cold    PVOH/Triton blend                                                                             91        4.8   3.1                                 7   Cold    ME-5/Surfynol blend                                                                           >270      4.2   3.5                                 8   Cold    ME-5/Triton blend                                                                             77        4.0   4.1                                 __________________________________________________________________________      .sup.a A 2:1 equivalent basis blend of Triton X100 and Triton X305. Trito      is an octylphenoxy polyethoxy ethanol marketed by Rohm and Haas.               .sup.b ME5 is Methocel ® E5, a hydroxypropyl methyl cellulose having       28-30% methoxyl substitution and a 7-12% hydroxypropoxyl substitution          marketed by Dow Chemical Co.                                             

EXAMPLE 2

Polymerization Runs 5-8 were repeats of Runs 1-4, respectively, with the exception that the "cold initiation" process was used. A premix comprising components 1-7 as described was charged to the reactor. After charging the premix to the reactor and purging with nitrogen, the temperature of the premix was adjusted to a temperature of about 32° C. and mixed for 30 minutes. The polymerization was initiated by addition of the reducing agent. After the premix temperature rose about 1° C. indicating the beginning of the exotherm, the addition of the delay feeds was commenced. The rate of reducing agent addition caused the reaction temperature to reach about 52° C. within about 30 minutes and the temperature was maintained at about 55° C. by the control addition of the reducing agent.

From the data presented in Table 1 it can be seen that the utilization of the cold initiation process according to the invention resulted in a remarkable improvement in the shear resistance of the pressure sensitive adhesive polymer compositions of Runs 5-8 compared to their hot initiated counterparts. The vinyl acetate/dioctyl maleate/acrylic acid/triallyl cyanurate (VAc/DOM/AA/TAC) emulsion using a polyvinyl alcohol/ethoxylated acetylenic diol stabilization system gave a shear resistance of 44 hours when hot initiated (Run 1) and a remarkable 232 hours when cold initiated (Run 5). Although the peel and loop tack values decreased by approximately 10% with the cold initiated emulsion, these properties were still quite acceptable. When the octylphenoxy polyethoxy ethanol blend was substituted for the ethoxylated acetylenic diol blend, the hot initiated Run 2 gave a relatively poor shear resistance of only 9 hours compared to about a 10 fold increased shear resistance of 91 hours for the cold initiated Run 6 which also showed a slight improvement in peel and loop tack properties.

The VAc/DOM/AA/TAC polymer emulsions prepared using hydroxypropyl methyl cellulose and polyethoxylated acetylenic diol as the stabilization system provided the best shear resistance properties. The hot initiated Run 3 pressure sensitive adhesive composition demonstrated a 124 hour shear resistance which jumped up to a startling duration of greater than 270 hours when the cold initiation process was performed in Run 7. The peel strength improved by about 10% while the loop tack strength was reduced about 20% although still within an acceptable commercial range. Substituting the octylphenoxy polyethoxy ethanols for the polyethoxylated acetylenic diols in combination with the hydroxypropyl methyl cellulose showed an improvement of about 165% in shear resistance when the cold initiation process of the invention was used. See Runs 4 and 8. Again the peel and loop tack properties were at an acceptable level.

EXAMPLE 3

In polymerization Runs 9-12 the cold initiation procedure of Example 2 was followed using the same amounts of monomers in various stabilization systems as set forth in Table 2.

                  TABLE 2                                                          ______________________________________                                                              SHEAR       180°                                                                          LOOP                                          STABILIZATION  RESISTANCE  PEEL  TACK                                    RUN   SYSTEM         (hr)        (lb)  (lb)                                    ______________________________________                                          9    HEC.sup.a /Surfynol                                                                           56.4        3.5   1.9                                     10    HPC.sup.b /Surfynol                                                                           18.6        3.9   1.7                                     11    Jaguar.sup.c /Surfynol                                                                        7.0         6.0   4.9                                     12    ME-5/Surfynol  >166        4.7   2.9                                     ______________________________________                                          .sup.a HEC is hydroxyethylcellulose, Natrosol 2502R marketed by Hercules,      Inc.                                                                           .sup.b HPC is hydroxypropylcellulose, Klucel E marketed by Hercules, Inc.      .sup.c Jaguar Gum A.sub.2 S a polysaccharide marketed by SteinHall & Co.,      Inc.                                                                     

From Table 2 it can be seen that Run 12, which was a repeat of Run 7 and used the hydroxypropyl methyl cellulose/polyethoxylated acetylenic diols stabilization system, resulted in a pressure sensitive adhesive polymer composition having a shear resistance of greater than 166 hours. The shear strength test was terminated at that time. The peel and loop tack properties were slightly less than that for corresponding Run 7. Run 9 which used a hydroxyethyl cellulose/polyethoxylated acetylenic diol stabilization system showed a shear resistance of about 56 hours. While the shear resistance of the composition prepared using polysaccharide and polyethoxylated acetylenic diols (Run 11) gave a relatively poor shear resistance of about 7 hours, the peel and loop tack strengths were much above that of the other runs. It is believed that the shear strengths of the corresponding copolymer compositions prepared using the typical hot initiated procedure would be significantly inferior.

STATEMENT OF INDUSTRIAL APPLICATION

The polymerization process of this invention provides pressure sensitive adhesive polymer compositions demonstrating enhanced shear resistance and suitable as adhesive coatings or for release liners, labels, decals and tapes. 

What is claimed is:
 1. In a process for preparing a pressure sensitive adhesive emulsion containing a polymer having a Tg of -10° C. or below which comprises polymerizing in an aqueous emulsion (a) an alkyl acrylate or vinyl ester, (b) an olefinically unsaturated carboxylic acid and (c) a polyolefinically unsaturated monomer for enhancing cohesive strength of the polymer, the method for enhancing the shear resistance of the pressure sensitive adhesive polymer which comprises(1) forming an aqueous suspension reaction mixture comprising a stabilizing agent and at least a portion of the alkyl acrylate or vinyl ester, (2) initiating the reaction mixture by the addition of a free radical source at a temperature from about 10°-40° C. and bringing the reaction mixture to a reaction temperature of from 45°-85° C. within a period of not more than about 2 hours with the reaction temperature exceeding the initiation temperature by at least 15° C., (3) adding the olefinically unsaturated carboxylic acid monomer and the polyolefinically unsaturated monomer at a substantially uniform rate such that the major portion of the carboxylic acid and polyolefinically unsaturated monomers has been added by the time the alkyl acrylate and vinyl ester content as free monomer in the reaction mixture has been reduced to a level of less than about 10 wt % of the mixture, and (4) continuing polymerization of the reaction mixture until the alkyl acrylate and vinyl ester content as free monomer in the reaction mixture is reduced below about 1 wt %.
 2. The method of claim 1 in which the reaction mixture temperature is from about 25° to 35° C. upon initiation.
 3. The method of claim 2 in which the reaction temperature is brought to about 45°-85° C. within a period of less than about 1 hour.
 4. The method of claim 3 in which the reaction temperature exceeds the initiation temperature by at least 20° C.
 5. The method of claim 4 in which the reaction mixture is brought to a reaction temperature of from 50°-60° C. within 1 hour.
 6. The method of claim 1 in which at least 10% of the alkyl acrylate and/or vinyl ester is added in step (1) and the remainder added in step (3).
 7. The method of claim 1 in which at least 50% of the alkyl acrylate and/or vinyl ester is added in step (1) and the remainder added in step (3).
 8. The method of claim 1 in which all of the alkyl acrylate, alpha,beta olefinically unsaturated dicarboxylic acid diester, olefinically unsaturated carboxylic acid and polyolefinically unsaturated monomer are added to the aqueous suspension reaction mixture prior to initiation.
 9. The method of claim 1 in which the oxidizing agent of a redox system is added in step (1) and the reducing agent of the redox system is added to initiate the reaction in step (2).
 10. The method of claim 1 in which the reducing agent of a redox system is added in step (1) and the oxidizing agent is added in step (2) to initiate the reaction.
 11. The method for preparing a pressure sensitive adhesive copolymer emulsion containing a copolymer having a T_(g) of -10° C. or below which consists essentially of(a) forming an aqueous suspension reaction mixture comprising a stabilizing agent and at least 10% of the total of an ester monomer which is a C₂ -C₁₀ alkyl ester of acrylic or methacrylic acid, a C₄ -C₁₄ diester of an alpha,beta olefinically unsaturated dicarboxylic acid or a vinyl ester of a C₁ -C₄ alkanoic acid and the reducing or oxidizing component of a redox system, (b) initiating the reaction mixture by the addition of the other component of the redox system at a temperature from about 10° to 40° C. and bringing the reaction mixture to a reaction temperature of from 45°-85° C. within a period of not more than about 2 hours with the reaction temperature exceeding the initiation temperature by at least 20° C., (c) adding a C₃ -C₆ olefinically unsaturated carboxylic acid monomer and a polyvinyl or polyallylic monomer at a substantially uniform rate such that the major portion of the caroxylic acid and polyvinyl or polyallylic monomers has been added by the time the ester monomer content as free monomer in the reaction mixture has been reduced to a level of less than about 10 wt % of the mixture, the combination of ester monomers, olefinically unsaturated carboxylic acid monomer, and polyvinyl or polyallylic monomer being selected to provide a copolymer having a T_(g) of -10° C. or below, and (d) continuing polymerization of the reaction mixture until the ester monomer content as free monomer in the reaction mixture is reduced below about 1 wt %.
 12. The method of claim 11 in which the reaction mixture is brought to a reaction temperature of from 45° to 85° C. within a period of not more than about one hour.
 13. The method of claim 12 in which the reaction temperature upon initiation is from about 25° to 35° C.
 14. The method of claim 13 in which the reaction mixture is brought to a reaction temperature of from 50° to 60° C.
 15. The method of claim 14 in which at least 50% of the ester monomers are present in the reaction mixture prior to initiation and the remainder added in step (c).
 16. In a process for preparing a pressure sensitive adhesive emulsion containing a copolymer having a Tg of -10° C. or below which comprises polymerizing in an aqueous emulsion (a) 57 to 67 wt % C₈ -C₂ alkyl diester of an alpha,beta-olefinically unsaturated dicarboxylic acid, (b) 32-42 wt % vinyl acetate, (c) 0.1 to 0.4 wt % polyallylic monomer and (d) 0.5 to 3 wt % olefinically unsaturated carboxylic acid, the method for enhancing the shear resistance of the pressure sensitive adhesive copolymer which comprises(1) forming an aqueous suspension reaction mixture comprising a stabilizing agent and at least 10% of the C₈ -C₁₂ alkyl diester of the alpha,beta-olefinically unsaturated dicarboxylic acid and vinyl acetate, (2) initiating the reaction mixture by the addition of a free radical source at a temperature from about 10°-40° C. and bringing the reaction mixture to a reaction temperature of from 45°-85° C. within a period of not more than about 1 hour with the reaction temperature exceeding the initiation temperature by at least 20° C., (3) adding the remaining diester and vinyl acetate, the olefinically unsaturated carboxylic acid monomer and the polyallylic monomer at a substantially uniform rate such that the major portion of the carboxylic acid and polyallylic monomers has been added by the time the diester and vinyl acetate content as free monomer in the reaction mixture has been reduced to a level of less than about 10 wt % of the mixture, and (4) continuing polymerization of the reaction mixture until the diester and vinyl acetate content as free monomer in the reaction mixture is reduced below about 1 wt %.
 17. The method of claim 16 in which the diester is dioctyl maleate and the olefinically unsaturated carboxylic acid is acrylic acid.
 18. The method of claim 17 in which the polyallylic monomer is triallylcyanurate.
 19. The pressure sensitive adhesive emulsion prepared according to claim
 1. 20. The pressure sensitive adhesive emulsion prepared according to claim
 4. 21. The pressure sensitive adhesive emulsion prepared according to claim
 11. 22. The pressure sensitive adhesive emulsion prepared according to claim
 15. 23. The pressure sensitive adhesive emulsion prepared according to claim
 16. 24. The pressure sensitive adhesive emulsion prepared according to claim
 18. 